Tertiary alcohol-bearing organosilicone polymers

Abstract

A particular class of tertiary alcohol substituted organosilicone polymers are provided which comprise chemically combined monofunctional siloxy units (Mo) and difunctional siloxy units (Do) and, for every two moles of Mo, an average of from about two to about 100 silicon-bonded tertiary alcohol groups (Q) and an average of from about 2 to about 30 silicon-bonded E DEG groups where E DEG is hydrogen or a polyoxyalkylene block (E). When E DEG is hydrogen, the polymers are tertiary alcohol-substituted polyalkylsiloxane hydrides and, when E DEG is E, the polymers are tertiary alcohol-substituted polyalkylsiloxane-polyoxyalkylene copolymers. The monofunctional siloxy units encompassed by Mo have at least two alkyls bonded to the respective silicon atoms thereof and the difunctional siloxy units encompassed by Do have at least one alkyl bonded to the respective silicon atoms thereof, the remaining group bonded to silicon of said Mo and Do units being alkyl, Q or E DEG . The tertiary alcohol-modified polyalkylsiloxane hydrides are especially useful as hydrosilation and condensation agents such as in forming the correspondingly modified polyalkylsiloxane-polyoxyalkylene copolymers of the invention. The copolymers in turn find particular application in the manufacture of cellular urethane products.

What is claimed is: 
     
       1. A tertiary alcohol -substituted organosiloxane polymer having the average formula, ##STR49## wherein: R is an alkyl radical having from one to ten carbon atoms; E° is hydrogen or a polyoxyalkylene block; Q is a tertiary alcohol group having the formula, ##STR50## wherein R 1  represents a bivalent hydrocarbon radical selected from the calss consisting of alkylene radicals having from 2 to 8 carbon atoms, alkenylene radicals having from 2 to 8 carbon atoms and dialkylene ether radicals having from 4 to 10 carbon atoms; wherein each R 2  radical taken individually represents a monovalent hydrocarbon radical having from 1 to 10 carbon atoms or where taken together form a cycloaliphatic radical with the tertiary carbon atom of the ##STR51## group, wherein t, u, v, w, the sum t+u and the sum v+w are independently zero or one, and each of the sums t+w and u+v is independently zero, one or two; x is zero or a positive number having an average value up to about 200; y has an average value from about 2 to about 100; and z has an average value from about 2 to about 30. 
     
     
       2. A siloxane polymer as defined in claim 1, wherein R 1  is selected from the group consisting of --CH 2  CH 2  --, --CH=CH-- and ##STR52## and each R 2  radical is a methyl radical. 
     
     
       3. A siloxane polymer as defined in claim 1, wherein E° is hydrogen. 
     
     
       4. A siloxane polymer as defined in claim 1, wherein E° is a polyoxyalkylene block. 
     
     
       5. A siloxane polymer as defined in claim 1, wherein x is a positive number. 
     
     
       6. A tertiary alcohol-substituted polyalkylsiloxane hydride as defined in claim 1 having the average formula ##STR53## wherein R 1  is selected from the group consisting of --CH 2  CH 2  --, --CH=CH-- and ##STR54## 
     
     
       7. A tertiary alcohol-substituted polyalkylsiloxane hydride as defined in claim 6, wherein R is an alkyl of one to four carbon atoms, and R 1  is --CH 2  CH 2  --. 
     
     
       8. A tertiary hydroxy-substituted polymethylsiloxane hydride as defined in claim 7 wherein R is methyl, x has an average value from about 20 to about 100, y has an average value from about 2 to about 30, and z has an average value no more than about 15. 
     
     
       9. A tertiary alcohol-substituted organosiloxane polymer as defined in claim 1 having the average formula ##STR55## wherein R 1  is selected from the group consisting of --CH 2  CH 2  --, --CH=CH-- and ##STR56## R°  comprises a bivalent alkylene radical a carbon atom of which is bonded to silicon; r is zero or one; G is an organic capping group; b has an average value from about 3 to about 100; z has a value from two to four provided at least 20 weight percent of --(OC 2  H 2a ) b  -- is constituted of oxyethylene; x is zero or a positive number having an average value of up to about 200; y has an average value from about 2 to about 100; and z has an average value from about 2 to about 30. 
     
     
       10. A siloxane polymer as defined in claim 9 wherein R is alkyl of one to four carbon atoms, x of said copolymer has an average value of at least about 10, and the average polyoxyalkylene content of --(OC a  H 2a ) b  -- is constituted of from about 20 to about 75 weight percent of oxyethylene. 
     
     
       11. A siloxane polymer as defined in claim 9, wherein R 1  is --CH 2  CH 2  -- and R is methyl. 
     
     
       12. A siloxane polymer is defined in claim 9, in which r of said copolymer is one. 
     
     
       13. A siloxane polymer as defined in claim 9, in which G of said copolymer is a monovalent hydrocarbon group having from 1 to 12 carbon atoms. 
     
     
       14. A siloxane polymer as defined in claim 9, in which G is alkyl of one to four carbon atoms. 
     
     
       15. A siloxane polymer as defined in claim 9, in which G is aryl. 
     
     
       16. A siloxane polymer as defined in claim 9, in which G is aralkyl. 
     
     
       17. A siloxane polymer as defined in claim 9, in which G is R°°C(O)-- where R°° is a monovalent hydrocarbon group having from 1 to 12 carbon atoms. 
     
     
       18. A siloxane polymer as defined in claim 9, in which G is R°°NHC(O)-- where R°° is a monovalent hydrocarbon group having from 1 to 12 carbon atoms. 
     
     
       19. A siloxane polymer as defined in claim 9, having the average formula ##STR57## wherein: Me is methyl; G is an organic capping group; e has a value from 2 to 6; x has an average value from about 10 to about 200; y has an average value from about 2 to about 100; z has an average value from about 2 to about 30; a has a value from two to four provided an average of from 20 to about 75 weight percent of --(OC a  H 2a ) b  -- is constituted of oxyethylene units; and b has an average value such that the average molecular weight of --(OC a  H 2a ) b  -- is from about 1000 to about 6000. 
     
     
       20. A siloxane polymer as defined in claim 19, having the average formula ##STR58## wherein R°° is a monovalent hydrocarbon group having one to twelve carbon atoms; x has an average value from about 20 to about 100; y has an average value from about 2 to about 30; z has an average value from about 2 to about 15; and m and n are positive numbers the average values of which are such that the average molecular weight of the chain, --(OC 2  H 4 ) n  (OC 3  H 6 ) m  --, is from about 1000 to about 6000 and the average oxyethylene content of said chain is from about 20 to about 65 weight percent. 
     
     
       21. A siloxane polymer as defined in claim 20, in which R°° of said copolymer is alkyl of one to four carbon atoms. 
     
     
       22. A siloxane polymer as defined in claim 21, in which R°° is methyl. 
     
     
       23. A siloxane polymer as defined in claim 22 having the average formula ##STR59## 
     
     
       24. A process for producing polyurethane foam which comprises reacting and foaming a reaction mixture containing: (a) an organic polyol reactant comprising a polyether polyol or a polyester polyol having an average of at least two hydroxyl groups per molecule; (b) an organic polyisocyanate reactant having at least two isocyanato groups per molecule; (c) a blowing agent; (d) a catalyst comprising an amine; and (e) a foam stabilizer comprising a polysiloxane-polyoxyalkylene copolymer having the average formula ##STR60## wherein: R is alkyl having from one to ten carbon atoms; t, u, v, w, the sum t+u and the sum v+w are independently zero or one, and each of the sums t+w and u+v is independently zero, one or two; Q is a tertiary alcohol group having the formula ##STR61## wherein R 1  represents a bivalent hydrocarbon radical selected from the class consisting of alkylene radicals having from 2 to 8 carbon atoms, alkenylene radicals having from 2 to 8 carbon atoms and dialkylene ether radicals having from 4 to 10 carbon atoms; wherein each R 2  radical taken individually represents a monovalent hydrocarbon radical having from 1 to 10 carbon atoms or where taken together form a cycloaliphatic radical with the tertiary carbon atom of the ##STR62## group and, when reactant (a) comprises a polyether polyol, x has an average value from about 10 to about 200, y has an average value from about 2 to about 100, z has an average value from about 2 to about 30, and E is a polyoxyalkylene block the average polyxoyalkylene content of which is constituted of from about 20 to about 75 weight percent of oxyethylene units; and, when reactant (a) comprises a polyester polyol, x is zero or a positive number having an average value up to about 20, y has an average value from about 2 to about 20, z has an average value from about 2 to about 30, and E is a polyoxyalkylene block the average polyoxyalkylene content of which is constituted of at least 75 weight percent oxyethylene units. 
     
     
       25. A process as defined in claim 24, in which said reaction mixture contains an organic flame-retardant as an additional component thereof. 
     
     
       26. A flame-retardant-containing flexible polyurethane foam produced by the process of claim 25. 
     
     
       27. A process for producing flexible polyether polyurethane foam which comprises simultaneously reacting and foaming a reaction mixture containing: (a) an organic polyol reactant comprising a polyether polyol having an average of at least two hydroxyl groups per molecule; (b) an organic polyisocyanate reactant containing at least two isocyanato groups per molecule; (c) water as a source of blowing action; (d) a catalyst comprising a tertiary-amine; and (e) a foam stabilizer comprising a polysiloxane-poly(oxyethylene-oxypropylene) copolymer having the average formula, ##STR63## wherein: R is alkyl having from one to four carbon atoms; R 1  is selected from the group consisting of --CH 2  CH 2  --, --CH=CH-- and ##STR64## R° comprises a bivalent alkylene group of from 2 to 6 carbon atoms a carbon atom of which is bonded to silicon; G is an organic capping group; r is zero or one; x has an average value from about 10 to about 200, y has an average value from about 2 to about 100, and z has an average value from about 2 to about 30, provided an average of from about 50 to about 85 weight percent of said copolymer is constituted of said --(R°) r  (OC 2  H 4 ) n  (OC 3  H 6 ) m  OG blocks; and m and n are numbers such that the average molecular weight of the chain --(OC 2  H 4 ) n  (OC 3  H 6 ) m  -- is from about 1000 to about 6000 and from about 20 to 65 weight percent of the chain is consituted of oxyethylene. 
     
     
       28. A process for producing flexible polyetherbased polyurethane foam containing a flame-retardant which comprises simultaneously reacting and foaming a reaction mixture containing: (a) a polyether polyol reactant containing an average of at least two hydroxyl groups per molecule; (b) an organic polyisocyanate reactant containing at least two isocyanato groups per molecule; (c) water as a source of blowing action; (d) a catalyst comprising a tertiary-amine; (e) a flame-retarding agent; and (f) a foam stabilizer comprising a tertiary alcohol-substituted polymethylsiloxane-poly(oxyethylene-oxypropylene) copolymer having the average composition, ##STR65## wherein: Me is methyl; G comprises a monovalent hydrocarbon group having foam 1 to 12 carbon atoms; x has an average value from about 20 to about 100, y has an average value from about 2 to about 30, and z has an average value from about 2 to about 15, provided the average weight of said copolymers attributable to said --C 3  H 6  (OC 2  H 4 ) n  (OC 3  H 6 ) m  OG groupings is from about 50 to about 85 weight percent; and m and n are numbers such that the average molecular weight of the chain, --(OC 2  H 4 ) n  (OC 3  H 6 ) m  --, is from about 1000 to about 6000 and from about 20 to about 65 weight percent of said chain is constituted of oxyethylene. 
     
     
       29. A flame-retardant-containing polyurethane foam produced by the process of claim 28.